CN114094126A - Preparation method of fuel cell catalyst, fuel cell catalyst and fuel cell - Google Patents
Preparation method of fuel cell catalyst, fuel cell catalyst and fuel cell Download PDFInfo
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Abstract
According to the preparation method of the fuel cell catalyst, a template agent, an initiator and a nitrogen-containing polymer precursor are dissolved in a water solution to obtain a first mixture, the first mixture is dispersed in a solution containing a rare earth metal precursor and an alkali metal salt and is stirred and adsorbed to obtain a second mixture, the second mixture is calcined at 600-1000 ℃ for 0.2-5h to obtain a sintered product, and the sintered product is dried in vacuum to obtain the fuel cell catalyst. The method has the advantages of simple process, low raw material cost, safety, reliability, environmental friendliness and the like.
Description
Technical Field
The present disclosure relates to the field of fuel cells, and more particularly, to a method for preparing a fuel cell catalyst, and a fuel cell.
Background
The high-entropy rare earth monatomic catalyst is a catalyst with excellent catalytic performance, which is formed by uniformly dispersing rare earth metal on a carrier in a monatomic form. At present, the research and application of the high-entropy rare earth monatomic catalyst are few, and the invention similar to the high-entropy rare earth monatomic catalyst comprises a noble metal monatomic catalyst (such as a platinum monatomic catalyst, a gold monatomic catalyst, a palladium monatomic catalyst and the like) and a transition metal monatomic catalyst (such as an iron monatomic catalyst, a cobalt monatomic catalyst, a nickel monatomic catalyst and the like). The noble metal catalysts are mainly currently faced with problems of high cost and deactivation by poisoning, while transition metal monatomic catalysts are difficult to exert excellent performance in fuel cells. Therefore, there is an urgent need for an efficient electrocatalyst with low cost, stable performance and environmental friendliness.
Disclosure of Invention
In view of this, it is necessary to provide a method for preparing a fuel cell catalyst with good ORR catalytic performance, aiming at the defect of poor ORR catalytic performance in the prior art.
In order to solve the above problems, the following technical solutions are adopted in the present application:
in one aspect, the present application provides a method for preparing a fuel cell catalyst, comprising the steps of:
dissolving a template agent, an initiator and a nitrogen-containing polymer precursor in an aqueous solution to obtain a first mixture;
dispersing the first mixture into a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture;
calcining the second mixture at 600-1000 ℃ for 0.2-5h to obtain a sintered product; and
and drying the sintered product in vacuum to obtain the fuel cell catalyst.
In some embodiments, the step of dissolving the template, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain the first mixture includes:
dissolving a template agent in an aqueous solution, adding an initiator after ultrasonic dissolution, adding a nitrogen-containing polymer precursor after stirring and dissolving, and then continuously stirring and aging the obtained solution for at least 24 hours to obtain a first mixture; when the template or the initiator is limited to be dissolved in the aqueous solution, the aqueous solution is added with an acid solution, and the acid solution comprises hydrochloric acid or sulfuric acid or nitric acid.
In some embodiments, in the step of dissolving the template agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain the first mixture, the template agent includes one or more of cetyltrimethylammonium bromide, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, octadecyl hydroxysultaine, polypropylenephthalein, polyethylene glycol, polyvinylpyrrolidone, polydextrose, polygarcinyl ester, various organic amines, and quaternary ammonium salt compounds.
In some of the embodiments, the initiator is at least one of a peroxide initiator or an azo initiator, the peroxide initiator comprises an organic peroxide or an inorganic peroxide, and the organic peroxide comprises an organic peroxide with a general structural formula of R-O-O-H or R-O-O-R, wherein R is an alkyl group, an acyl group or a carbonate group; the inorganic peroxide comprises ammonium persulfate or potassium persulfate or sodium persulfate; the azo initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate.
In some embodiments, the nitrogen-containing polymer precursor may be one or more of pyrrole, pyridine, pyrazole, imidazole, thiazole, pyrimidine, quinoline, purine, aniline, and derivatives thereof.
In some embodiments, the molar concentration ratio of the template agent to the initiator to the nitrogen-containing polymer precursor is 1:1 to 6:4 to 50.
In some embodiments, in the step of dispersing the first mixture in a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture, specifically:
and alternately filtering and washing the first mixture by using water and ethanol to remove the template agent and the precursor with low polymerization degree, dispersing the template agent and the precursor with low polymerization degree into a solution containing a rare earth metal precursor and an alkali metal salt, and stirring and adsorbing to obtain a second mixture.
In some of these embodiments, the alkali metal salt can be any one or more soluble alkali metal salts selected from one or more of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium sulfate, lithium carbonate, lithium acetate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium iron phosphate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium sulfate, sodium carbonate, sodium acetate, sodium perchlorate, sodium hexafluoroarsenate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium ferric phosphate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium sulfate, potassium carbonate, potassium acetate, potassium perchlorate, potassium hexafluoroarsenate, potassium hexafluorophosphate, potassium tetrafluoroborate, and potassium ferric phosphate.
In some of these embodiments, the rare earth metal precursor comprises soluble salts of at least 5 metals selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium in MClx, MIx、MBrx、MFx、M(NO3)x、Mx(SO4)y、M(Ac)x、Mx(PO4)y、Mx(C2O4)yWherein M is Sc, Y, La, Ce, Pr, Nd, Pm Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; x is 2,3, 4; and y is a hydrate of a rare earth metal salt of 2,3,4 or more.
In some embodiments, the molar concentration ratio of the rare earth metal precursor to the alkali metal salt in the solution is 1: 2-20, the sum of the molar concentrations of the rare earth metal precursors is 1-1000 mmol/L, and the content of each rare earth metal precursor is any proportion other than 0.
In some of these embodiments, the second mixture is first subjected to N at a temperature of 600 ℃ to 1000 ℃2Calcining for 0.2-5h, and then NH3The intermediate calcination is carried out for 0.2-5h to obtain a sintered product, and the steps are as follows:
carrying out suction filtration and vacuum drying on the second mixture, uniformly grinding the second mixture to obtain a solid sample, and putting the solid sample in N2Heating to 600-1000 ℃ under air flow, and calcining for 0.2-5 h; after cooling to room temperature, the solid powder obtained is taken to NH3Heating to 600-1000 ℃ under the air flow, calcining for 0.2-5h, and cooling to room temperature to obtain a sintered product.
In some embodiments, the step of vacuum drying the sintered product to obtain the fuel cell catalyst specifically includes:
and (2) pickling the sintered product at 40-80 ℃ for 2-8h, performing suction filtration after washing to obtain a solid sample, performing vacuum drying on the solid sample, pickling the obtained product, and performing vacuum drying again to obtain the fuel cell catalyst.
In another aspect, the present application also provides a fuel cell catalyst prepared by the preparation method of the fuel cell catalyst.
In still another aspect, the present application also provides a fuel cell to which the fuel cell catalyst is added.
According to the preparation method of the fuel cell catalyst, a template agent, an initiator and a nitrogen-containing polymer precursor are dissolved in a water solution to obtain a first mixture, the first mixture is dispersed in a solution containing a rare earth metal precursor and an alkali metal salt and is stirred and adsorbed to obtain a second mixture, the second mixture is calcined at 600-1000 ℃ for 0.2-5h to obtain a sintered product, and the sintered product is dried in vacuum to obtain the fuel cell catalyst. The method has the advantages of simple process, low raw material cost, safety, reliability, environmental friendliness and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the description of the embodiments of the present application or the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart illustrating the steps of a method of making a fuel cell catalyst provided herein;
FIG. 2 is a scanning electron microscope picture of the HE (La/Ce/Pr/Nd/Pm) catalytic material prepared in example 1 of the present application;
FIG. 3 shows the loading of the electrode with the catalytic material prepared in examples 1-5 of the present application at 0.22mg/cm2The ORR performance of the test is compared with that of the test (the test condition is that a three-electrode system, a working electrode is a catalyst, a counter electrode is a carbon rod, a reference electrode is a saturated calomel electrode, and an electrolyte is 0.1mol/L KOH solution);
FIG. 4 is a comparative ORR performance diagram of the high-entropy rare earth (La/Ce/Pr/Nd/Pm) electro-catalyst in example 1 (test conditions: three-electrode system, working electrode is catalyst, counter electrode is carbon rod, reference electrode is saturated calomel electrode, electrolyte is 0.1mol/L KOH solution).
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary and intended to be used for explaining the present application and should not be construed as limiting the present application.
In the description of the present application, it is to be understood that the terms "upper", "lower", "horizontal", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present application and simplifying the description, and do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments.
Referring to fig. 1, a flow chart of steps of a method for preparing a fuel cell catalyst according to an embodiment of the present application includes the following steps:
step S110: dissolving a template agent, an initiator and a nitrogen-containing polymer precursor in an aqueous solution to obtain a first mixture.
In some embodiments, a template agent is dissolved in an aqueous solution, an initiator is added after ultrasonic dissolution, a nitrogen-containing polymer precursor is added after stirring dissolution, and the obtained solution is stirred and aged for at least more than 24 hours to obtain a first mixture; when the template or the initiator is limited to be dissolved in the aqueous solution, the aqueous solution is added with an acid solution, and the acid solution comprises hydrochloric acid or sulfuric acid or nitric acid.
Further, the template may be: cetyl Trimethyl Ammonium Bromide (CTAB), Sodium Dodecyl Sulfate (SDS), Sodium Dodecyl Benzene Sulfonate (SDBS), octadecyl hydroxy sulfobetaine (DHSB), Polyacrylamide (PAM), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polydextrose, polygaret, various organic amines, and one or more of quaternary ammonium salt compounds.
Further, the initiator is at least one of a peroxide initiator or an azo initiator, the peroxide initiator comprises an organic peroxide or an inorganic peroxide, the organic peroxide comprises an organic peroxide with a structural general formula of R-O-O-H or R-O-O-R, wherein R is an alkyl group, an acyl group or a carbonate group; the inorganic peroxide comprises ammonium persulfate or potassium persulfate or sodium persulfate; the azo initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate.
For example, the organic peroxide may include the following: such as benzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, etc.
Further, the nitrogen-containing polymer precursor can be one or more of pyrrole, pyridine, pyrazole, imidazole, thiazole, pyrimidine, quinoline, purine, aniline and derivatives of the above compounds.
Further, the molar concentration ratio of the template agent to the initiator to the nitrogen-containing polymer precursor is 1: 1-6: 4-50.
It can be understood that the coordination environment of the high-entropy rare earth monoatomic catalyst can be adjusted by changing the type and the dosage of the polymer precursor, the type and the content of the rare earth elements and the like, and the electronic structure of the active center is improved, so that the adjustment of the performance of the rare earth monoatomic catalyst is realized.
Step S120: and dispersing the first mixture into a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture.
In some embodiments, the first mixture is alternately filtered and washed by water and ethanol to remove the template agent and the low-polymerization-degree precursor, and then dispersed in a solution containing a rare earth metal precursor and an alkali metal salt, and stirred and adsorbed to obtain a second mixture.
Specifically, the alkali metal salt may be any one or more soluble alkali metal salts, and the soluble alkali metal salt is one or more of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium sulfate, lithium carbonate, lithium acetate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium iron phosphate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium sulfate, sodium carbonate, sodium acetate, sodium perchlorate, sodium hexafluoroarsenate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium iron phosphate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium sulfate, potassium carbonate, potassium acetate, potassium perchlorate, potassium hexafluoroarsenate, potassium hexafluorophosphate, potassium tetrafluoroborate, and potassium iron phosphate.
Specifically, the rare earth metal precursor may be: soluble salts comprising at least 5 metals selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).
The rare earth metal precursor provided by the application comprises soluble salts of at least 5 metals, so that the symmetry of a carbon ring is broken, a large pi bond is broken, the regulation and control activity of a carbon substrate is enhanced, and the catalytic performance is synergistically increased by multiple elements.
Specifically, the soluble salt is MClx, MIx, MBrx, MFx, M (NO3) x, Mx (SO4) Y, M (Ac) x, Mx (PO4) Y, Mx (C2O4) Y (wherein M is Sc, Y, La, Ce, Pr, Nd, Sm Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, x is 2,3,4, Y is 2,3,4) or a hydrate of the above rare earth metal salt.
Specifically, the molar concentration ratio of the rare earth metal precursor to the alkali metal salt in the solution is 1: 2-20, the sum of the molar concentrations of the rare earth metal precursors is 1-1000 mmol/L, and the content of each rare earth metal precursor is not 0 at any ratio.
It is understood that the presence of a specific rare earth monoatomic atom can be ensured and the generation of metal clusters or nanoparticles can be avoided in this concentration range.
Step S130: and calcining the second mixture at 600-1000 ℃ for 0.2-5h to obtain a sintered product.
In some of these examples, the second mixture is suction filtered and vacuum dried and then ground uniformly to obtain a solid sample, which is then ground to N2Heating to 600-1000 ℃ under air flow, and calcining for 0.2-5 h; after cooling to room temperature, willThe solid powder obtained is taken to NH3Heating to 600-1000 ℃ under the air flow, calcining for 0.2-5h, and cooling to room temperature to obtain a sintered product.
Step S140: and drying the sintered product in vacuum to obtain the fuel cell catalyst.
In some embodiments, the sintered product is subjected to acid washing at 40-80 ℃ for 2-8h, after washing, a solid sample is obtained through suction filtration, the solid sample is subjected to vacuum drying, the obtained product is subjected to acid washing, and vacuum drying is performed again to obtain the fuel cell catalyst.
According to the preparation method of the fuel cell catalyst provided by the embodiment of the application, the high-entropy rare earth monatomic catalyst prepared by organic polymerization and high-temperature calcination has the advantages of small diameter, small aperture, high porosity, good fiber uniformity and the like, has good ORR catalytic performance, and can be widely applied to fuel cells and metal air cells.
The method has the advantages of simple process, low raw material cost, safety, reliability, environmental friendliness and the like; the prepared fuel cell catalyst modifies materials by a plurality of rare earth elements in a single atom form to improve the electrocatalytic activity of the materials, so that the electrocatalytic activity of the substrate materials is greatly improved; meanwhile, a plurality of rare earth elements are introduced into the polymer fiber, and the nano electro-catalyst which is modified by high-entropy rare earth single atoms and has abundant surface defects is obtained after high-temperature pyrolysis and acid treatment, and shows excellent performance in electro-catalysis ORR.
The raw materials used in the above practical preparation method of the present invention are as described in the foregoing examples, and are not described herein again.
The following examples are provided to further illustrate the preparation of the high entropy rare earth monatomic catalyst.
Example 1
The preparation method of the high-entropy rare earth metal monatomic catalyst comprises the following steps:
s1: dissolving 0.1g CTAB (template) into 1mol/L HCl, adding 1.73g APS (initiator), stirring to dissolve, adding 1mL pyrrole (nitrogen-containing polymer precursor), and continuously stirring for 24 h;
s2: after washing with water and ethanol alternately for 3 times, the obtained solid material was dispersed in a medium containing 0.4mol/L LiCl and LaCl in an amount of 100mL3、CeCl3、PrCl3、NdCl3And Pmcl3In a solution with the concentration of 4mmol/L, stirring and adsorbing for 24 hours after ultrasonic dispersion for 30 min;
s3: filtering the product obtained in S2, vacuum drying to obtain a solid sample, heating the solid sample to 900 ℃, and sequentially adding N2And NH3Calcining for 0.5 h;
s4: the obtained sample is used for 150ml of 1mol/L H2SO4Washing twice, filtering, and drying in vacuum to obtain the La/Ce/Pr/Nd/Pm high-entropy rare earth monatomic catalyst.
Comparative example 1
CTAB as template agent, APS as initiator, LiNO3As the alkali metal salt, pyrrole was used as a precursor of the nitrogen-containing polymer, and EuCl was used at a concentration of 4mmol/L3、GdCl3、TbCl3、DyCl3And HoCl3As the rare earth metal precursor, the KOH concentration in the electrochemical test was 0.1mol/L, and the electrochemical test was carried out with reference to example 1.
Comparative example 2
SDS is taken as a template agent, potassium persulfate is taken as an initiator, LiCl is taken as an alkali metal salt, pyrrole is taken as a nitrogen-containing polymer precursor, and LaCl with the concentration of 4mmol/L3、CeCl3、PrCl3、NdCl3And Pmcl3As the rare earth metal precursor, the KOH concentration in the electrochemical test was 0.1mol/L, and the electrochemical test was carried out with reference to example 1.
Comparative example 3
CTAB as template agent, potassium persulfate as initiator, NaNO3As the alkali metal salt, aniline is used as a precursor of the nitrogen-containing polymer, and LaNO with the concentration of 4mmol/L is used3、CeNO3、PrNO3、NdNO3And PmNO3As the rare earth metal precursor, the KOH concentration in the electrochemical test was 0.1mol/L, and the electrochemical test was carried out with reference to example 1.
Comparative example 4
CTAB is taken as a template agent, APS is taken as an initiator, NaCl is taken as an alkali metal salt, aniline is taken as a nitrogen-containing polymer precursor, and ScCl with the concentration of 4mmol/L is adopted3、PrCl3、EuCl3、HoCl3And YbCl3As the rare earth metal precursor, the KOH concentration in the electrochemical test was 1mol/L, and the electrochemical test was carried out with reference to example 1.
Referring to fig. 2, fig. 3 and fig. 4, the high-entropy rare earth metal monatomic catalyst obtained in the above-mentioned embodiment is assembled into a three-electrode system, and the ORR test is performed with the catalyst as a working electrode, a carbon rod as a counter electrode, a saturated calomel electrode as a reference electrode, and an electrolyte as a 0.1mol/L KOH solution, wherein the catalyst loading is 0.22mg/cm2, and the voltage range is 1.0V-0.4V vs. rhe (the same test method is adopted in the subsequent embodiments of the present invention to obtain the electrochemical performance results). The test results and other parameters are shown in table 1.
TABLE 1
As can be seen from table 1, in the embodiment 1 of the present invention, CTAB is selected as a template, APS is selected as an initiator, and chloride salts of La, Ce, Pr, Nd, Pm are selected as rare earth metal precursors, which shows a higher initial potential and a higher half-wave potential, and has good ORR performance.
Examples 2 to 76
Examples 2 to 76 differ from example 1 only in the kind or content of the rare earth metal precursor, and specifically, as shown in table 2, the ORR test was performed on the high-entropy rare earth metal monatomic catalysts obtained in examples 5 to 76, and the test results are shown in table 2:
TABLE 2
As can be seen from Table 2, when soluble salts of Ce or Y are added, the catalyst has better ORR performance and shows higher initial potential and half-wave potential.
Examples 77 to 103
Examples 77 to 103 differ from example 1 only in the kind of the templating agent, and specifically, as shown in table 3, the high entropy rare earth metal monatomic catalyst obtained in examples 77 to 103 was subjected to the ORR test, and the test results are shown in table 3:
Sc/Y/La/Ce/Pr/Nd/Pm/Sm/Eu/Gd/Tb/Dy/Ho/Er/Tm/Yb/Lu
TABLE 3
As can be seen from Table 3, CTAB as a template agent, the catalyst has better ORR performance, and shows higher initial potential and half-wave potential.
Example 104-
The difference between the example 104-122 and the example 1 is only the kind of the initiator, and specifically as shown in table 4, the ORR test is performed on the high-entropy rare earth metal monatomic catalyst obtained in the example 104-122, and the test results are shown in table 4:
TABLE 4
As can be seen from table 4, when APS was used as the initiator, the catalyst had better ORR performance, and exhibited higher initial potential and half-wave potential.
Example 123-
Example 123-152 differs from example 1 only in the type of nitrogen-containing polymer precursor, and specifically as shown in table 5, the ORR test was performed on the high-entropy rare earth metal monatomic catalyst obtained in example 123-and the test results are shown in table 5:
TABLE 5
As can be seen from Table 5, when pyrrole is used as the precursor of the nitrogen-containing polymer, the catalyst has better ORR performance and shows higher initial potential and half-wave potential.
Example 153-
Example 153-differing from example 1 only in the kind of alkali metal salt, specifically as shown in table 6, the high entropy rare earth metal monatomic catalyst obtained in example 153-was subjected to the ORR test, and the test results thereof are shown in table 6:
TABLE 6
As can be seen from Table 6, the alkali metal salt is lithium chloride, and the catalyst has better ORR performance and shows higher initial potential and half-wave potential.
The high-entropy rare earth monatomic catalyst related to the embodiment of the invention is not limited to a three-electrode system when being applied, and can also be applied to fuel cells. The important component of the embodiment of the invention is a rare earth monoatomic electrocatalyst synthesized by a plurality of rare earth elements and distributed in high entropy, which has good stability while maintaining good ORR performance. The method is also an important preparation method and application of the monatomic catalyst, which are developed while the electrocatalyst has lower cost because the rare earth metal is prepared in the high-entropy monatomic form for the first time.
The foregoing is considered as illustrative only of the preferred embodiments of the invention, and is presented only for the purpose of illustrating the principles of the invention and not in any way to limit its scope. Any modifications, equivalents and improvements made within the spirit and principles of the present application and other embodiments of the present application without the exercise of inventive faculty will occur to those skilled in the art and are intended to be included within the scope of the present application.
Claims (14)
1. A method of preparing a fuel cell catalyst, comprising the steps of:
dissolving a template agent, an initiator and a nitrogen-containing polymer precursor in an aqueous solution to obtain a first mixture;
dispersing the first mixture into a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture;
calcining the second mixture at 600-1000 ℃ for 0.2-5h to obtain a sintered product; and
and drying the sintered product in vacuum to obtain the fuel cell catalyst.
2. The method for preparing a fuel cell catalyst according to claim 1, wherein in the step of dissolving the templating agent, the initiator, and the nitrogen-containing polymer precursor in an aqueous solution to obtain the first mixture, specifically:
dissolving a template agent in an aqueous solution, adding an initiator after ultrasonic dissolution, adding a nitrogen-containing polymer precursor after stirring and dissolving, and then continuously stirring and aging the obtained solution for at least 24 hours to obtain a first mixture; when the template or the initiator is limited to be dissolved in the aqueous solution, the aqueous solution is added with an acid solution, and the acid solution comprises hydrochloric acid or sulfuric acid or nitric acid.
3. The method of claim 2, wherein the template comprises one or more of cetyltrimethylammonium bromide, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, octadecyl hydroxysultaine, polyacrylamide, polyethylene glycol, polyvinylpyrrolidone, polydextrose, polybehenate, various organic amines, and quaternary ammonium salt compounds.
4. The method of claim 2, wherein the initiator is at least one of a peroxide initiator or an azo initiator, the peroxide initiator comprises an organic peroxide or an inorganic peroxide, and the organic peroxide comprises an organic peroxide having a general structural formula of R-O-H or R-O-R, wherein R is an alkyl group, an acyl group, a carbonate group; the inorganic peroxide comprises ammonium persulfate or potassium persulfate or sodium persulfate; the azo initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate.
5. The method of claim 2, wherein the nitrogen-containing polymer precursor is one or more of pyrrole, pyridine, pyrazole, imidazole, thiazole, pyrimidine, quinoline, purine, aniline, and derivatives thereof.
6. The method for preparing a fuel cell catalyst according to claim 2, wherein the molar concentration ratio of the template agent, the initiator and the nitrogen-containing polymer precursor is 1:1 to 6:4 to 50.
7. The method for preparing a fuel cell catalyst according to claim 1, wherein in the step of dispersing the first mixture in a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture, specifically:
and alternately filtering and washing the first mixture by using water and ethanol to remove the template agent and the precursor with low polymerization degree, dispersing the template agent and the precursor into a solution containing a rare earth metal precursor and an alkali metal salt, and stirring and adsorbing to obtain a second mixture.
8. The method for preparing a fuel cell catalyst according to claim 7, wherein the alkali metal salt is any one or more soluble alkali metal salts selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium sulfate, lithium carbonate, lithium acetate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium iron phosphate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium sulfate, sodium carbonate, sodium acetate, sodium perchlorate, sodium hexafluoroarsenate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium ferric phosphate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium sulfate, potassium carbonate, potassium acetate, potassium perchlorate, potassium hexafluoroarsenate, potassium hexafluorophosphate, potassium tetrafluoroborate, and potassium ferric phosphate.
9. The method of claim 7, wherein the rare earth metal precursor comprises a soluble salt of at least 5 metals selected from the group consisting of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, wherein the soluble salt is MClx, MI, and lutetiumx、MBrx、MFx、M(NO3)x、Mx(SO4)y、M(Ac)x、Mx(PO4)y、Mx(C2O4)yWherein M is Sc, Y, La, Ce, Pr, Nd, Pm Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; x is 2,3, 4; and y is a hydrate of a rare earth metal salt of 2,3,4 or more.
10. The method for preparing a fuel cell catalyst according to claim 9, wherein the molar concentration ratio of the rare earth metal precursor to the alkali metal salt in the solution is 1:2 to 20, the sum of the molar concentrations of the rare earth metal precursors is 1 to 1000mmol/L, and the content of each rare earth metal precursor is not 0 at any ratio.
11. The method of preparing a fuel cell catalyst according to claim 1, wherein the second mixture is first subjected to N at a temperature of 600 ℃ to 1000 ℃2Calcining for 0.2-5h, and then NH3The intermediate calcination is carried out for 0.2-5h to obtain a sintered product, and the steps are as follows:
carrying out suction filtration and vacuum drying on the second mixture, uniformly grinding the second mixture to obtain a solid sample, and putting the solid sample in N2Heating to 600-1000 ℃ under air flow, and calcining for 0.2-5 h; after cooling to room temperature, the solid powder obtained is taken to NH3Heating to 600-1000 ℃ under the air flow, calcining for 0.2-5h, and cooling to room temperature to obtain a sintered product.
12. The method for preparing a fuel cell catalyst according to claim 1, wherein the step of vacuum-drying the sintered product to obtain the fuel cell catalyst specifically comprises:
and (2) pickling the sintered product at 40-80 ℃ for 2-8h, performing suction filtration after washing to obtain a solid sample, performing vacuum drying on the solid sample, pickling the obtained product, and performing vacuum drying again to obtain the fuel cell catalyst.
13. A fuel cell catalyst produced by the method for producing a fuel cell catalyst according to any one of claims 1 to 12.
14. A fuel cell characterized by being added with the fuel cell catalyst according to claim 13.
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